CN102318111A - Catalytic electrode with gradient porosity and catalyst density for fuel cells - Google Patents

Catalytic electrode with gradient porosity and catalyst density for fuel cells Download PDF

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CN102318111A
CN102318111A CN2010800048636A CN201080004863A CN102318111A CN 102318111 A CN102318111 A CN 102318111A CN 2010800048636 A CN2010800048636 A CN 2010800048636A CN 201080004863 A CN201080004863 A CN 201080004863A CN 102318111 A CN102318111 A CN 102318111A
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layer
catalyst
multilayer
bark paper
ground floor
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CN102318111B (en
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郑建平
梁智勇
王奔
张春
朱伟
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Florida State University Research Foundation Inc
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Florida State University Research Foundation Inc
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8636—Inert electrodes with catalytic activity, e.g. for fuel cells with a gradient in another property than porosity
    • H01M4/8642—Gradient in composition
    • H—ELECTRICITY
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    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8892—Impregnation or coating of the catalyst layer, e.g. by an ionomer
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    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
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    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • C—CHEMISTRY; METALLURGY
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Abstract

A membrane electrode assembly (110) for a fuel cell (100) comprising a gradient catalyst structure (120 or 140) and a method of making the same. The gradient catalyst structure (120 or 140) can include a plurality of catalyst nanoparticles, e. g. , platinum, disposed on layered buckypaper. The layered buckypaper can include at least a first layer and a second layer and the first layer can have a lower porosity compared to the second layer. The gradient catalyst structure (120 or 140) can include single-wall nanotubes, carbon nanofibers, or both in the first layer of the layered buckypaper and can include carbon nanofibers in the second layer of the layered buckypaper. The membrane electrode assembly (110) can have a catalyst utilization efficiency of at least 0. 35 gcat/kW or less.

Description

The catalysis electrode that is used for fuel cell with gradient porosity and density of catalyst
About the research of federal government's subsidy or the statement of exploitation
According to No. 023106 contract between the research of AUS Communication Electronics, exploitation and engineering center and Florida State Univ., U.S. government has right in this invention.
Technical field
The present invention relates to be used for the field of the membrane electrode assembly of Proton Exchange Membrane Fuel Cells.
Background technology
Fuel cell is thought promising power source and other main body portable and fixed-purpose that is used for installing (comprising automobile) on a large scale by many people.Fuel cell can provide high-energy source efficient and comparatively faster startup.In addition, fuel cell can produce electric power under the situation that does not produce various environmental pollutions (this is the characteristic of many other power sources).Therefore, fuel cell is the solution that satisfies crucial energy demand, and fuel cell also alleviates environmental pollution through replacing source powered by conventional energy simultaneously.
Although the increase of fuel cells applications has brought some advantages, whether its wide range of commercialization then possibly depend on can reduce unit power cost relevant with fuel cell (noble metal cost) and reduction degree thereof.For transport applications, USDOE (DOE) has set 2015 technical indicators of eelctro-catalyst, promptly at 0.2mg/cm 2Total Pt load factor under produce 1W/cm 2Rated power, obtain the Pt utilance (USDOE's " hydrogen fuel cell and infrastructure technical plan-spend for many years research, exploitation and demonstration project " (2007)) of 0.2gpt/kg.The utilance of this level will have considerable benefit, comprise owing to fuel cell identical or that improve export required platinum (Pt) amount reduce cause cost significantly to reduce.In fact, realize that a business-like promising especially approach is to improve the Pt utilance also to optimize electrode structure simultaneously, so that obtain higher Pt specific power density.
Yet an obstacle realizing this purpose is in the conventional catalyst carrier material (like carbon black Vulcan XC-72R) many micropores that can fetter the Pt nano particle to be arranged.This causes setting up the three phase boundary between gas, electrolyte and eelctro-catalyst (TPB) of fuel cell usually.Therefore, can not utilize the appropriate section (because electrochemical reaction can not take place) of Pt, thereby cause Pt to utilize the decline of level at these positions.In addition, can be etched under the intrinsic harsh conditions of carbon black in fuel battery negative pole, thereby cause the low and shortening in useful life of stability test.
Recently, investigated CNT and nanofiber possibility, because carbon nanomaterial shows higher conductivity and bigger specific area usually as the catalyst carrier in the Proton Exchange Membrane Fuel Cells (PEMFC).In addition, this carbon nanomaterial has relatively low microporosity and shows excellent electrochemical corrosion resistant property usually.
Make the common process of employed catalyst layer based on CNT and carbon nano-fiber in the Proton Exchange Membrane Fuel Cells (PEMFC); Be that CNT (CNT) or carbon nano-fiber (CNF) are scattered in the adhesive (like Teflon or Nafion) and form slurry, use this slurry coating gas diffusion layer then.Yet, in the common process intrinsic prominent question be to add adhesive in the fabrication stage to be easy to make the CNT in the electrocatalyst layers to separate, thereby cause the relatively poor electron transport performance and the degeneration or the elimination of Pt active surface.
Summary of the invention
Therefore, in view of above-mentioned background, a characteristic of the present invention provides a kind of membrane electrode assembly based on material with carbon element above-mentioned limiting factor, that be used for fuel cell (MEA) that overcomes.According to an aspect of the present invention, membrane electrode assembly comprises near the porous multilayer Bark paper film of band catalyst nanoparticles (be arranged on the surface of the Bark paper with special gradient-structure or).Term " Bark paper " used in this literary composition is meant a kind of membranaceous stability of composite materials, and this composite material comprises the network of SWCN (SWNT), multi-walled carbon nano-tubes (MWNT), carbon nano-fiber (CNF) or its combination.With the catalyst layer of Bark paper-nano-particle catalyst composite material as membrane electrode assembly (MEA).
According to the present invention, gradient pore-size distribution and catalyst nanoparticles that a concrete characteristic of membrane electrode assembly (MEA) is based on multilayer Bark paper (LBP) film that has the ground floor and the second layer at least distribute.Can make multilayer Bark paper by CNT, nanofiber or its mixture using little binder or not using under the situation of adhesive.
Through adjustment parent material and nanoparticle dispersion liquid, can customize out the microstructure of multilayer Bark paper (LBP), thereby obtain porosity, aperture, surface area and the conductivity of the expectation of membrane electrode assembly (MEA) catalyst layer.Preferably, catalyst nanoparticles directly is deposited on the position of the full blast of multilayer Bark paper, makes the phase reaction Coefficient Maximization thus.With compare with the fuel cell of conventional method manufacturing, the membrane electrode assembly of making in the above described manner can have higher catalyst utilization in electrode, higher power output can be provided, can have the non-oxidizability of enhancing and longer useful life.
In one embodiment, membrane electrode assembly disclosed herein can comprise PEM and gradient catalyst structure.The gradient catalyst structure can comprise a plurality of catalyst nanoparticles that are arranged on the multilayer Bark paper that comprises the ground floor and the second layer at least.Catalyst structure can comprise gradient-structure, makes multilayer Bark paper ground floor have the porosity that is lower than the multilayer Bark paper second layer.The catalyst utilization of a plurality of catalyst nanoparticles of membrane electrode assembly can be equal to or less than 0.35g Cat/ kW.
The multilayer Bark paper of ground floor can comprise the mixture of SWCN (SWNT) and carbon nano-fiber (CNF), and the multilayer Bark paper of the second layer can comprise carbon nano-fiber (CNF).
After forming multilayer Bark paper, can a plurality of catalyst nanoparticles be deposited on the multilayer Bark paper.Said a plurality of catalyst nanoparticles can comprise platinum (Pt).Catalyst layer is deposited on the perfluorinated sulfonic resin on the multilayer Bark paper after also can being included in and forming multilayer Bark paper.
Below, above these execution modes and other execution mode are made more detailed description.
Brief Description Of Drawings
Illustrate preferred embodiment in the accompanying drawings.Yet, should be noted that the present invention is not limited to accurate layout and the means shown in the accompanying drawing.
Fig. 1 is the sketch map that comprises the exemplary in nature proton exchange film fuel cell (PEMFC) of membrane electrode assembly (MEA).
Fig. 2 (a)-Fig. 2 (d) is the image and the energy dispersive X-ray data of exemplary multilayer Bark paper, and wherein Fig. 2 (a) is scanning electron microscopy (SEM) image of exemplary multilayer Bark paper section; Fig. 2 (b) is that the energy dispersive X-ray spectrum (EDS) of the multilayer Bark paper of Fig. 2 (a) is analyzed; Fig. 2 (c) is the surface image of the multilayer Bark paper ground floor of Fig. 2 (a); Fig. 2 (d) is the surface image of the multilayer Bark paper second layer of Fig. 2 (a).
Fig. 3 is the battery polarization curve of membrane electrode assembly (MEA) with exemplary gradient catalyst structure (as cathode catalyst layer) and as the power density of the function of current density.
Fig. 4 (a) is the polarization curve of membrane electrode assembly (MEA) with exemplary gradient catalyst structure and as the battery polarization curve of the power density of the function of current density and two conventional membrane electrode assemblies (MEA) with as the power density of the function of current density.
Fig. 4 (b) is voltage and the graph of a relation of mass activity (mass activity) of the membrane electrode assembly of Fig. 4 (a).
Fig. 4 (c) is electrochemical impedance spectrum (EIS) data of the membrane electrode assembly of Fig. 4 (a).
Fig. 5 is the figure of the fuel cell of band exemplary film electrode assemblie at the polarization curve of different operating time.
Fig. 6 (a) is transmission electron microscope (TEM) image of exemplary multilayer Bark paper.
Fig. 6 (b) is the Pt particle size distribution of the exemplary multilayer Bark paper of Fig. 6 (a).
Fig. 7 (a) and 7 (b) are the figure of the electrochemical properties of exemplary film electrode assemblie (MEA) and conventional membrane electrode assembly (MEA).
Fig. 8 (a) is electrochemical impedance spectrum (EIS) data with membrane electrode assembly and two conventional membrane electrode assemblies of exemplary gradient catalyst structure.
Fig. 8 (b) is the improvement Randles-Ershler equivalent-circuit model that is used to measure the electrochemical impedance spectroscopic data of Fig. 8 (a).
Embodiment
Herein disclosed is newly-designed the have membrane electrode assembly (MEA) of the fuel cell of gradient catalyst structure and the method that is used to make this assembly.Adopt the layered carbon nano material Bark paper of band catalyst nanoparticles in the membrane electrode assembly.Multilayer Bark paper can manufacture and make it have gradient pore-size distribution, gradient porosity, gradient electrolyte concentration and/or the distribution of gradient catalyst nanoparticles.
Used " nano particle " is meant the particle of long axis length less than 300nm in this literary composition.Long axis length can be less than 200nm or less than 100nm.The long axis length of the catalyst nanoparticles described in this paper can be in the scope of 0.1nm to 100nm or 0.1nm to 50nm or 1nm to 25nm or 1nm to 10nm.
Fig. 1 shows the exemplary in nature proton exchange film fuel cell (PEMFC) 100 that uses membrane electrode assembly disclosed herein.Membrane electrode assembly 110 can comprise anode catalyst layer 120, PEM 130 and cathode catalyst layer 140.PEM 130 plays anode catalyst layer 120 and cathode catalyst layer 140 is separated the effect that allows the electrical insulator that proton 145 passes through simultaneously again.In addition, membrane electrode assembly (MEA) 110 can comprise anode gas diffusion layer 150 and cathode gas diffusion layer 160.Anode catalyst layer 120 can be electrically connected to electromechanical assembly 170 with cathode catalyst layer 140, makes electronics to flow to cathode catalyst layer 140 through electromechanical assembly 170 from anode catalyst layer 120.Exemplary electrochemical appliance 170 includes but not limited to motor, electrical socket and electrical energy storage device (like storage battery and capacitor).
In one embodiment, the anode-side 180 with Proton Exchange Membrane Fuel Cells (PEMFC) 100 is designed so that fuel gas 190 is (like hydrogen (H 2)) contact with anode catalyst layer 120.Then, used fuel 200 is discharged from the outlet of anode-side 180.The cathode side 210 of Proton Exchange Membrane Fuel Cells (PEMFC) 100 is designed so that oxidant 220 is (like airborne oxygen (O 2)) contact with cathode catalyst layer 140.Oxygen can produce water and produce heat 240 in the oxidation of cathode side 210.The mixture 230 of air and water flows out cathode side 210, can utilize the air of water, cooling or other hot swapping to remove excessive heat 240 simultaneously.Certainly, though disclose exemplary Proton Exchange Membrane Fuel Cells, also exist other Proton Exchange Membrane Fuel Cells (PEMFC) design that to adopt membrane electrode assembly disclosed herein.
As shown in fig. 1, anode catalyst layer 120 and cathode catalyst layer 140 can be arranged in the relative both sides of PEM 130.Anode catalyst layer 120 can be arranged between anode gas diffusion layer 150 and the PEM 130.Cathode catalyst layer 140 can be arranged between cathode gas diffusion layer 160 and the PEM 130.Anode catalyst layer 120 can be that separate or integrally formed with anode gas diffusion layer 150.Cathode catalyst layer 140 can be that separate or integrally formed with cathode gas diffusion layer 160.
Membrane electrode assembly (MEA) catalyst structure can comprise catalyst nanoparticles (for example Pt) and the solid electrolyte (for example polymer) on the outer surface that gathers group at the interface and/or at catalyst that is distributed in cathode catalyst layer 140 and/or the anode catalyst layer 120 separately with PEM 130, in order to the reinforcement active site and reduce the proton transport resistance.In addition, membrane electrode assembly (MEA) can comprise little Pt/C and gather group, thereby helps reactant to arrive active site.
The electrode layer 120 and/or 140 that membrane electrode assembly disclosed herein (MEA) can comprise PEM 130 and comprise the gradient catalyst structure, said gradient catalyst structure comprise the multilayer Bark paper that is furnished with a plurality of catalyst nanoparticles on it.Multilayer Bark paper can have the ground floor and the second layer at least, and wherein the porosity of ground floor is lower than the second layer.Membrane electrode assembly can have and is equal to or less than 0.4g at least Cat/ kW, be equal to or less than 0.35g Cat/ kW, be equal to or less than 0.3g Cat/ kW, be equal to or less than 0.25g Cat/ kW or be equal to or less than 0.2g CatThe catalyst utilization of/kW.With respect to the membrane electrode assembly of routine,, has catalyst utilization ratio in the improved electrode, higher power output, better non-oxidizability and longer useful life according to the membrane electrode assembly of design disclosed herein.
Used term " Bark paper " is meant that membranaceous stability of composite materials, this composite material comprise the network of SWCN (SWNT), multi-walled carbon nano-tubes (MWNT), carbon nano-fiber (CNF) or its combination in this literary composition.In execution mode disclosed herein,, can stablize Bark paper largely through resilient single-walled nanotube and/or many walls of minor diameter nanotube are wrapped on the nanofiber and/or many walls of major diameter nanotube that has more rigidity more greatly.
Multilayer Bark paper can comprise at least by the different dispersions of the various combination of different nano materials, nano material or nano material constituted two-layer.Nano material can comprise nanotube or nanofiber at least.
Used term " CNT " and write a Chinese character in simplified form " nanotube " and be meant to have and be generally columniform shape and have usually about 840 in this literary composition to carbon fullerene structure greater than the molecular weight in 1,000 ten thousand dalton's scopes.CNT is to buy from for example carbon Nanosolutions GmbH (Carbon Nanotechnologies Inc.) (Houston, Texas, the U.S.), perhaps can utilize technology known in the art to make.Single-walled nanotube can have less than the diameter of 5 nanometers and the length between 100 to 1000 nanometers.Many walls nanotube is many wall constructions, and can have less than the diameter in 10 nanometer to 100 nanometer range with in the length between 500 nanometers and 500 millimeters.Carbon nano-fiber is to have the cylindrical shape nanostructure that is arranged in pile up coniform, cup-shaped or laminal graphene layer, and can have the diameter of 50 nanometer to 200 nanometers and 30 millimeters to 100 millimeters length.
Term " minor diameter multi-walled carbon nano-tubes (MWNT) " used in this literary composition is meant that diameter is equal to or less than many walls nanotube of 10nm, and term " major diameter multi-walled carbon nano-tubes (MWNT) " is meant the many wall nanotube of diameter greater than 10nm.The minor diameter multi-walled carbon nano-tubes can have the diameter that is at least 0.1nm.
Used " porosity " is material or the hole of layer or the volume shared ratio in the cumulative volume of material or layer in gap that percentage is represented in this literary composition.The porosity of multilayer Bark paper ground floor can be than the porosity low at least 5%, 10%, 15%, 20%, 30% or 40% of the multilayer Bark paper second layer.For example, the porosity of ground floor can be 75%, and the porosity of the second layer can be 80%, thereby the porosity of ground floor is littler by 5% than the porosity of the second layer.The illustrative methods of measuring porosity comprises mercury injection method, gas adsorption method, optical method and direct method.
Through adjusting the microstructure that parent material and nano material dispersion liquid can customize out multilayer Bark paper, to obtain goal porosity, aperture, surface area and conductivity.For example, the gradient catalyst structure of membrane electrode assembly can comprise the multilayer Bark paper that has the ground floor and the second layer at least.Ground floor can comprise small size nano material and macro nanometer mixtures of material, and wherein (i) small size nano material can comprise SWCN, many walls of minor diameter nanotube or both; (ii) the macro nanometer material can comprise carbon nano-fiber, many walls of major diameter nanotube or both.The second layer can comprise carbon nano-fiber, many walls of major diameter nanotube or both.Except that carbon nano-fiber or many walls of major diameter nanotube or both, the second layer can also comprise single-walled nanotube or many walls of major diameter nanotube or both.
Therefore, perhaps both all can comprise multilayer Bark paper (that is gradient catalyst structure) for cathode catalyst layer 140, anode catalyst layer 120.The ground floor of multilayer Bark paper can comprise the mixture of single-walled nanotube and carbon nano-fiber, and the second layer can comprise carbon nano-fiber.The void fraction percent of ground floor can be than the void fraction percent low at least 5%, at least 10%, at least 15% or at least 20% of the second layer.The void fraction percent of ground floor can lowly be not more than 40% than the void fraction percent of the second layer, be not more than 35% or be not more than 30%.For example, the porosity of ground floor can be 40%, and the porosity of the second layer can be 80%, this means the porosity low 40% of the porosity of ground floor than the second layer.
Catalyst nanoparticles can comprise platinum, iron, nitrogen, nickel, carbon, cobalt, copper, palladium, ruthenium, rhodium and combination thereof.Catalyst nanoparticles can be platinum or platinum (111) or Pt 3Ni (111).
Can catalyst nanoparticles be distributed on the multilayer Bark paper by following mode: the catalyst nanoparticles of first weight percent is arranged on the ground floor, the catalyst nanoparticles of second weight percent is arranged on the second layer.Can calculate first weight percent and second weight percent through any suitable mode.For example, first weight percent can be to be arranged in the income value of the weight of the catalyst nanoparticles on the ground floor divided by the total weight of Bark paper ground floor.First weight percent of catalyst nanoparticles can be than the high at least 5wt% of second weight percent, 10wt%, 15wt%, 20wt%, 30wt% or 40wt% (representing with weight percent).This value that exceeds of computes capable of using:
(wt%-the 2nd wt%)/(wt%+ the 2nd wt%) * 100%
Therefore, be 2.5wt% if first weight percent is the 5wt% and second weight percent, first weight percent is than the high 33.3wt% of second weight percent (100% * (5-2.5)/(5+2.5)) so.
Membrane electrode assembly (MEA) can comprise Pt as a plurality of catalyst nanoparticles on the multilayer Bark paper (Pt/LBP) that is arranged in anode catalyst layer 120 or cathode catalyst layer 140.Fig. 2 shows the image of the exemplary gradient catalyst structure of Pt/LBP, and wherein ground floor comprises SWCN (SWNT) and carbon nano-fiber (CNF), and the second layer only comprises carbon nano-fiber (CNF).Fig. 2 (a) is scanning electron microscopy (SEM) image of multilayer Bark paper (LBP), and the thin ground floor (about 5 μ m) that is presented at the left side among the figure is compared with the second layer on the right, has lower porosity and average pore size.Fig. 2 (b) is that the EDS of Pt/LBP analyzes, and the figure illustrates the density distribution of Pt.Utilize coating process that most of Pt nano particle is deposited on the surface of the SWNT/CNF network in the ground floor.Fig. 2 (c) is the surface image of ground floor (SWNT/CNF mixture), shows a large amount of Pt nano particle depositions among the figure from the teeth outwards, and Fig. 2 (d) is the surface image of the second layer (CNF), shows less Pt nano particle deposition among the figure from the teeth outwards.
The gradient catalyst structure of anode cathode catalyst layer 120 and cathode catalyst layer 140 also can comprise solid catalyst, like ionomer.The exemplary ion polymer comprises perfluorinated sulfonic resin.Can be after the multilayer Bark paper of formation with a plurality of catalyst nanoparticles, the applying solid catalyst.Perfluorinated sulfonic resin also can distribute with concentration gradient along the thickness direction of multilayer Bark paper.Confirmed that the catalyst and the electrolytical load factor that keep suitable are the key factors that obtains good catalyst utilization.Therefore, the ground floor of multilayer Bark paper can be rich in catalyst nanoparticles and perfluorinated sulfonic resin, and the second layer of multilayer Bark paper can have the catalyst nanoparticles and the perfluorinated sulfonic resin of low concentration.The perfluorinated sulfonic resin that is used for membrane electrode assembly disclosed herein comprises: by E.I.Du Pont Company (with trade mark NAFION), by Dow Chemical company (with trade mark DOW), the perfluorinated sulfonic resin sold by Asahi Glass company (with trade mark FLEMION), by Asahi Chemical company (with trade mark ACIPLEX), perhaps any other suitable perfluorinated sulfonic resin substitute.
Membrane electrode assembly (MEA) can comprise PEM 130, gradient catalyst structure 120 and/or 140 and gas diffusion layers (GDL) 150 and/or 160.The gradient catalyst structure can comprise a plurality of catalyst nanoparticles that are arranged on the multilayer Bark paper; Wherein multilayer Bark paper has the ground floor and the second layer at least; Ground floor can have the porosity that is lower than the second layer, and membrane electrode assembly can have and is equal to or less than 0.3g at least CaJThe catalyst utilization of/kW.Can gradient catalyst structure 120 and/or 140 be oriented makes the ground floor of multilayer Bark paper 120 and/or 140 contact with PEM 130 and the second layer of multilayer Bark paper contacts with gas diffusion layers 150 and/or 160.
Membrane electrode assembly can comprise the gradient catalyst structure as negative electrode, anode or both.Preferably, membrane electrode assembly comprises gradient catalyst structure disclosed herein, at least as cathode layer.
The advantage of gradient catalyst structure disclosed herein comprises: (1) catalyst nanoparticles is positioned at the most accessible outer surface of multilayer Bark paper, thereby makes the catalyst utilization maximization; (2) aperture of gradient catalyst structure generally be in medium size (meso size) to the scope of macro-size (macro size); Thereby can be covered effectively by the perfluorinated sulfonic resin electrolyte, this helps to make the three phase boundary maximization that electrochemical reaction takes place; And (3) connect the passage that good porous nanometer material network can guarantee to be used for mass transfer and electric charge transfer.Be surprised to find that to have the gradient catalyst structure of catalyst nanoparticles distribution, porosity distribution and the solid electrolyte (for example perfluorinated sulfonic resin) of non-homogeneous (being gradient), can improve battery performance and catalyst utilization widely.
Though for embodiment of the present invention is unnecessary; But reason that it is generally acknowledged above-mentioned benefit is (at least in part); In the ground floor and the interface between the PEM 130 of the gradient catalyst structure of catalyst layer 120 and/or 140; Most of catalyst nanoparticles is distributed in the position near PEM 130, thereby the migration path that causes proton to arrive catalyst shortens.Higher solid electrolyte (for example perfluorinated sulfonic resin) load factor has also increased the contact area between the electrolyte phase in this two media.Therefore, improve the proton transfer restriction of proton with two kinds of methods.In addition, on the second layer and the interface between gas diffusion layers 150 and/or 160 of gradient catalyst layer 120 and/or 140, bigger hole and lower solid electrolyte load factor have reduced the possibility that solid electrolyte blocks the hole respectively.This helps to get rid of through the gaseous diffusion of gas diffusion layers 150 and/or 160 and water.Another advantage is the corrosion resistance that the good chemical stability of ground floor (for example carbon nano-tube/carbon nano fabric layer) can improve electrode greatly, thereby forms more stable electrode.
A unexpected characteristic of membrane electrode assembly 110 disclosed herein is fabulous utilances that they show the catalyst on the multilayer Bark paper that is arranged in gradient negative electrode and/or anode catalyst layer 140 and/or 120.Two interesting catalyst efficiency measurement indexes comprise (i) surface area utilance and (ii) catalyst utilization.The surface area utilance of the catalyst nanoparticles of the disclosed catalyst layer of this paper can be at least 60% or at least 65% or at least 70% or at least 75% or at least 75% or at least 80% or at least 85%.The catalyst utilization of the catalyst nanoparticles of the disclosed catalyst layer of this paper can be equal to or less than 0.50gPt/kW, or be equal to or less than 0.45gPt/kW, or is equal to or less than 0.40gPt/kW, or is equal to or less than 0.35gPt/kW, or is equal to or less than 0.30gPt/kW, or is equal to or less than 0.25gPt/kW, or is equal to or less than 0.20gPt/kW.
In this literary composition used " catalyst utilization " be the catalyst cupport rate divided by in membrane electrode assembly under 80 ℃ of temperature under the 0.65V the fuel of 20 pounds/square inch (psi) and the merchant of the battery power output under the oxidizing gas back pressure.
Used " surface area utilance " is with amassing (ECSA) (hereinafter) divided by the real surface that is calculated like formula (2) merchant of long-pending (hereinafter) like the electrochemical surface that utilizes formula (1) to be calculated among this paper.Formula (1) is the Scherrer formula, and is as follows:
D ( nm ) = 0.9 λ β 1 / 2 cos θ - - - ( 1 )
Wherein, D is the average grain diameter of Pt particle, λ be X ray wavelength (Cu Ka line,
Figure BPA00001406322700102
), β 1/2Be the half peak breadth (representing with radian) of Pt (111), θ is and the corresponding angle in (111) peak.Suppose that all particles are uniform spherical, the real surface that can calculate Pt in order to following equation is long-pending:
SA = surfacearea mass = π D 2 1 6 π D 3 ρ = 6 ρD - - - ( 2 )
Wherein, ρ is the mass density (21.4g/cm of Pt -3), D is the average diameter of Pt particle in the catalyst.
The invention still further relates to a kind of method of making the membrane electrode assembly of fuel cell.This method can comprise through forming multilayer Bark paper makes a plurality of catalytic nanoparticles be deposited on the method for making the gradient catalyst structure on the multilayer Bark paper then.Multilayer Bark paper can comprise the ground floor and the second layer at least, and ground floor can have the porosity that is lower than the second layer.
Multilayer Bark paper can comprise nano material, like SWCN, multi-walled carbon nano-tubes, carbon nano-fiber or its mixture.As previously mentioned, ground floor can comprise small size nano material and macro nanometer mixtures of material, and the second layer can comprise the macro nanometer material.Can utilize multiple technologies (including but not limited to electrochemical deposition, sputtering sedimentation, overcritical deposition and electronation) that a plurality of catalyst nanoparticles are deposited on the multilayer Bark paper.
After forming multilayer Bark paper, a plurality of catalyst nanoparticles are deposited on the multilayer Bark paper, can form the gradient catalyst structure thus.Can use less than 1wt% or less than 0.5wt% or less than 0.25wt% or less than the adhesive of 0.1wt%,, form multilayer Bark paper like TEFLON or NAFION.After the adhesive with minimum forms multilayer Bark paper, make the catalyst nanoparticles deposition, can make catalyst nanoparticles directly be deposited on the position of the full blast of multilayer Bark paper, thereby make the phase reaction Coefficient Maximization.Among this paper used " adhesive " be meant during Bark paper forms, add, in order between the nano wire that constitutes Bark paper, to produce the compound and the composition of adhesion.Exemplary adhesive comprises perfluorinated polymers, like the perfluorinated polymers of being sold by E.I.Du Pont Company (E.I.Du Pont De Nemours and Company is with trade mark EFLON); And perfluorinated sulfonic resin, like the perfluorinated sulfonic resin of selling by E.I.Du Pont Company (with trade mark AFION).
In case form, then can the gradient catalyst structure be incorporated in the film exchange assembly 110.For example, can anode catalyst layer 120, cathode catalyst layer 140 or both be pressed on the PEM 130.With solid electrolyte (like NAFION) coat gradient catalyst structure 120 and 140 and/or operation on the PEM 130 can before or after being incorporated into component sets film exchange assembly 110, carry out.After forming multilayer Bark paper, coat gradient catalyst structure 120 and/or 140 last times, solid electrolyte (for example perfluorinated sulfonic resin) plays a part to increase proton arrives cathode catalyst layer 140 through PEM 130 from the catalyst nanoparticles of anode catalyst layer 120 proton conductivity.All of a sudden, in this technology, incorporate solid electrolyte into, can make surface area utilance (utilance %) and catalyst utilization (g at this point Cat/ kW) significantly increase.
Embodiment
Embodiment 1
Under vacuum, 25wt% SWCN (SWNT)/75wt% carbon nano-fiber (CNF) suspension and carbon nano-fiber (CNF) suspension are filtered in order, prepare exemplary gradient catalyst structure thus.Shown in Fig. 2 (a); Carbon nano-fiber is wrapped with randomly; Thereby form porosity and be 90.8% and average pore size be the highly porous second layer of 85nm, and the SWCN that adds the fine sizes of 25wt% forms less hole in SWCN/carbon nano-fiber layer.As a result, because SWCN (SWNT) has big draw ratio, so SWCN (SWNT)/carbon nano-fiber (CNF) ground floor has the surface area (24m than carbon nano-fiber (CNF) layer 2/ g) much bigger surface area (105m 2/ g).Utilizing after electrochemical deposition is deposited on Pt on the multilayer Bark paper; The analysis of energy dispersive X-ray spectrum (EDS) among Fig. 2 (b) shows the Gradient distribution of Pt, and the Pt above 70% is distributed in SWCN (SWNT)/carbon nano-fiber (CNF) ground floor of 7 micron thick.Shown in Fig. 2 (c) and Fig. 2 (d), there is a large amount of Pt to be deposited on the surface of ground floor SWCN/carbon nano-fiber, there is less Pt nano particle to be deposited on the surface of second layer carbon nano-fiber simultaneously.Therefore, qualitative indication and quantitatively indication that Fig. 2 provides Pt in multilayer Bark paper, how to distribute are because the distribution of Pt in each layer is quite uniform.The surface topography image shows that Pt is more prone on the surface of SWCN rather than on carbon nano-fiber, grow.It is generally acknowledged that this is because SWCN has much bigger surface area and more blemish, thereby form the positioning of anchor that more is used for the Pt nucleation.Yet, to compare with the chemical reduction method that is used for the Pt deposition, electrochemical deposition causes having the relatively large Pt particle (average diameter: 5.4nm) of obviously gathering group.
Before being applied on the membrane electrode assembly, Pt/ multilayer Bark paper (LBP) impregnated in 5%Nafion solution in a vacuum, and is then dry down to import the proton conduction phase at 80 ℃.Under identical preparation condition, the load factor of Nafion estimates to be about 0.2g/cm in multilayer Bark paper 3And at conventional individual layer SWCN/carbon nano-fiber (1: 3wt./wt.) in the Bark paper be 0.29g/cm 3, therefore think that the Gradient distribution of Nafion appears at along Bark paper thickness direction, wherein, its less hole is arranged in SWCN/carbon nano-fiber layer owing to having more Nafion, and this helps to be used for absorption of N afion solution through capillary force.
Through using Pt/LBP gradient catalyst structure disclosed herein as cathode catalyst layer, the available relatively low Pt load factor of exemplary film electrode assemblie (MEA) demonstrates excellent power-performance.As shown in Figure 3, power-performance and Pt load can be at 0.11mg/cm 2Negative electrode Pt load factor under produce and to be at least 0.88W/cm 2The rated power of (under 0.65V).Total Pt utilance is 0.18gPt/kW (negative electrode and an anode), this near or surpass 2015 indexs of USDOE.
Embodiment 2
Although the Pt particle diameter is relatively large, the Pt/ multilayer Bark paper (LBP) with customization gradient-structure has demonstrated the stability of promising Pt utilance and carrier.Can ignore in view of the improvement that the antianode oxygen reduction reaction (ORR) that uses Pt/ multilayer Bark paper (LBP) is active, this high battery performance is considered to caused by the microstructure of the invention of gradient catalyst structure.In order to estimate the effect of microstructure, compare with regard to polarization curve and electrochemical impedance (EIS) aspect individual layer Bark paper membrane electrode assembly to two kinds of routines to fuel battery performance.Conventional Bark paper is by the mixture of SWCN and carbon nano-fiber (weight ratio is 1: 3, is called SF13, or weight ratio 1: 9, is called SF19) formation, and thickness is 14 μ m.Because be under the same conditions Pt to be deposited on respectively on each conventional Bark paper and the Pt/ multilayer Bark paper (LBP), each conventional Bark paper and Pt/ multilayer Bark paper (LBP) have catalyst nanoparticles size much at one.Nafion is immersed on conventional the Bark paper and Pt/ multilayer Bark paper (LBP); Yet, the difference of the pore structure of Nafion load factor Yin Bake paper and difference.
Shown in Fig. 4 (a), find based on the mass transfer limitations in the polarization curve of the membrane electrode assembly of SF13 in the intermediate current district (＞0.5A/cm 2) more remarkable.Fig. 4 (c) has shown that expression has tangible gas diffusion resistance at the impedance camber line based on the electrochemical impedance spectroscopy low frequency range of the membrane electrode assembly of SF13, thereby its reason is Nafion the obstruction in hole has been limited oxygen delivery and water eliminating.In membrane electrode assembly, do not find same mass transfer limitations, even in SWCN (SWNT)/carbon nano-fiber (CNF) ground floor of multilayer Bark paper, the obstruction to the hole has taken place based on Pt/ multilayer Bark paper (LBP).This can be interpreted as, and the macropore in the highly porous carbon nano-fiber second layer is difficult for being blocked by Nafion, thereby helps gaseous diffusion and draining.
Shown in Fig. 4 (b), in three kinds of catalyst structures, Pt/ multilayer Bark paper (LBP) is presented at the minimum charge transfer resistance (R under the high overpotential CT) and mass activity, this shows and has formed maximum active site/units that is used for oxygen reduction reaction (interface between the ionomer of Pt and diafiltration).It is active that the Gradient distribution of catalyst nanoparticles helps in Pt/ multilayer Bark paper (LBP), to form relative higher quality; Because most of catalyst nanoparticles is arranged on the thin SWCN/carbon nano-fiber ground floor of multilayer Bark paper, thereby presses close to or contact PEM.This has reduced the possibility that proton does not reach catalyst nanoparticles (ion resistance) widely.Therefore; The microstructure of invention with porosity, catalyst concn and electrolyte density of functional gradient; All of a sudden improve the transmission restriction of proton and reactant in Pt/ multilayer Bark paper (LBP) catalyst structure, thereby produced outstanding catalyst efficiency.
Embodiment 3
The durability research of the SWCN that is used for Proton Exchange Membrane Fuel Cells/nanofiber Bark paper catalyst carrier of accomplishing people such as W.Zhu (Journal of the Electrochemical Society " electrochemistry society journal (2009)); Under the accelerated degradation test condition in the fuel battery cathode with proton exchange film environment of simulation, SWCN (SWNT)/carbon nano-fiber (CNF) the Bark paper with Pt catalyst nanoparticles shows favorable durability.Reason that it is generally acknowledged good durability is the high-graphitized highly corrosion resistant that causes because of carbon nano-fiber.Subsequently; According to the testing scheme of describing in " hydrogen fuel cell and infrastructure technologies plan-are spent research, exploitation and demonstration plan for many years " (2007) of USDOE, estimate the durability of the catalyst carrier of the disclosed membrane electrode assembly based on Pt/ multilayer Bark paper (LBP) of this paper.Fig. 5 is presented at during the endurance test in 200 hours the polarization curve in different time-histories.Work 200 hours after under 900mV mensuration mass activity only lost 57.6% of initial activity; This is more better than the mass activity that obtains among the conventional Pt/C (lost initial activity 90%), and near 2015 indexs of USDOE (loss≤initial activity 60%).This result shows that the gradient catalyst structure is the good potential candidate of catalyst carrier, can obtain to have the high stability electrode of excellent catalysts efficient.
Embodiment 4
The preparation and the character of multilayer Bark paper (LBP)
Diameter is that 0.8-1.2nm and length are that the SWCN of 100-1000nm is to buy from carbon Nanosolutions GmbH (Carbon Nanotechnologies Inc.).The diameter of buying from applied science Co., Ltd (Applied Sciences Inc.) is that 100-200nm and length are the carbon nano-fiber of 30-100 μ m, and it is also followed 3,000 ℃ of high-temperature process through chemical vapor deposition (CVD) and makes.All material need not to be further purified and directly uses.
Utilize vacuum filtration manufactured multilayer Bark paper.Usually, at 500mL N, 10 milligrams of SWCNs (SWNT) in the dinethylformamide (Aldrich company) and carbon nano-fiber (CNF) (wt./wt.=1: 3) carry out 30 minutes ultrasonic Treatment, to obtain uniform suspension.Also prepared the suspension that only comprises the 10mg carbon nano-fiber.Then, under vacuum, SWCN (SWNT)/carbon nano-fiber (CNF) and carbon nano-fiber (CNF) suspension are filtered in order with nylon leaching film (Millipore, the aperture is 0.45 μ m).After drying, thin layer is peeled off from filter membrane, and produced the multilayer Bark paper of the carbon nano-fiber layer of the SWCN/carbon nano-fiber layer with ground floor and the second layer.Also can only filter the suspension of a type by the same manner, and preparation individual layer Bark paper.On individual layer Bark paper, carry out surface analysis.Use Tristar 3000 (Micrometritics) to measure Brunauer-Emmelt-Teller (BET) surface area with the nitrogen adsorption method.Use AutoPore 9520 systems of Micromeritics company to press the mercury porosity measurement, to confirm pore-size distribution.
The preparation of Pt/LBP and character
Utilize impulse electrodeposition technology (pulse electrodeposition technique) from 10mMH 2PtCl 6, 0.1M H 2SO 4With the mixed solution of 0.5M ethylene glycol at N 2Under the gas bell, the Pt nano particle is deposited on the multilayer Bark paper.Blank Bark paper work electrode is placed on the self-control specimen holder that has connected as the hydrophobicity carbon fiber paper of current-collector.As reference electrode, use work to electrode on the Pt net saturated calomel electrode (SCE).The electro-deposition area of Bark paper is 5cm 2, the Bark paper on the window ara that is placed on specimen holder is exposed in the electrolyte.Make the current potential that applied increase to-0.35 volt (with respect to saturated calomel electrode) from 0.3 volt with 4 seconds pulse durations, pulse duty factor is 25%.Repeat to give pulse, until the Pt load capacity that reaches expectation.Weight difference through before and after the weighing deposition is confirmed the Pt load capacity.
Utilize scanning electron microscopy (SEM, JEOL JSM 7401F) to come the surface and the cross section pattern of qualitative Pt/ multilayer Bark paper (LBP).Utilize three ion beam skiving appearance (Leica EM TIC020) to prepare the cross section sample.Utilization is attached to the energy dispersive X-ray spectrometer (EDS) on the JSM 7401F microscope, on the cross section of Pt/LBP, carries out the element distribution image scanning of platinum (Pt).(TEM, JEM-2010 JEOL) observe meticulous pattern, and Fig. 6 (a) has shown the transmission electron microscope image of Pt/ multilayer Bark paper (LBP) to utilize transmission electron microscope.Fig. 6 (b) has shown the Pt particle size distribution of being analyzed by the Pt particle that 150 are selected at random that transmission electron microscope image obtained.
In three electrodes/Room battery, adopt cyclic voltammetry (CV) to confirm that the electrochemical surface of Pt/ multilayer Bark paper (LBP) catalyst is long-pending.For the preparation work electrode, a Pt/LBP is bonded at glass carbon (GC) electrode (0.196cm with a 0.5%Nafion solution 2) the top.Electrolyte solution is 0.5M H 2SO 4, utilize 30 minutes nitrogen bubbles that this electrolyte solution is thoroughly outgased.Test period keeps nitrogen atmosphere above solution.The scope of current potential is-0.25 volt to+1.1 volts (with respect to a saturated calomel electrode), and sweep speed is 50mV/s.Under the room temperature at O 2Saturated 0.1M HClO 4In, utilize rotating disk electrode (r.d.e) (RDE) to measure oxygen reduction reaction (ORR) activity of Pt/ multilayer Bark paper (LBP).With the sweep speed of 10mV/s, under the rotating speed between 400 to 1600rpm, the linear voltammogram of record in the scope of 0-0.75 volt (with respect to saturated calomel electrode).
The manufacturing and the character of membrane electrode assembly (MEA)
All adopt double-decker as gas diffusion layers at cathode side and anode-side.Skin is the carbon paper (TGPH-090, Toray company) that has covered polytetrafluoroethylene (at negative electrode is the polytetrafluoroethylene of 30wt%, is the polytetrafluoroethylene of 10wt% at anode).With carbon black (Vulcan XC-72; Cabot company) isopropanol mixture with the ptfe emulsion (Aldrich company) of 30wt% or 10wt% is sprayed on the carbon paper; 340 ℃ of following sintering 1 hour, prepare internal layer (between carbon paper and catalyst layer) thus then.Utilize the conventional method of the use of ink and water (ink process) preparation anode catalyst layer.(20%Pt E-Tek) mixes in isopropyl alcohol with 10wt%Nafion on Vulcan XC-72, on the gas diffusion layers, forms 0.05mg/cm in being ejected into the air gunite then with the Pt/C catalyst of appropriate amount 2The anode catalyst layer of Pt load factor.Then, the Nafion solution (0.5mg/cm that one deck is approached 2) be sprayed on the surface of anode catalyst layer.Under vacuum, flood Pt/ multilayer Bark paper (LBP) with 5%Nafion solution (Aldrich company).After 80 ℃ of following dryings, Pt/ multilayer Bark paper (LBP) is placed on plays catalyst layer on the cathode gas diffusion layer, wherein the selected side with multilayer Bark paper (being SWCN/carbon nano-fiber layer) exposes.Finally, dielectric film (Nafion 212, Dupont company) is clipped between anode and the negative electrode, under 130 ℃ of temperature with 30kg/cm 2Pressure it is carried out hot pressing in 3 minutes, form membrane electrode assembly thus.Operate membrane electrode assembly by fuel battery test system (fuel cell technology), use the humidification hydrogen as fuel and use to add wet oxygen as oxidant.Fuel battery temperature is 80 ℃, H 2/ O 2The humidifier temperature is 80/80 ℃, and the back pressure in the fuel cell both sides is 20 pounds/square inch.It is 2: 3 stoichiometry level that flow rate is set at hydrogen and oxygen.The electronic load that utilization is assemblied in the test macro carries out record to battery performance.Use Solartron 1280B electrochemical workstation (Solartron) in constant current mode, in the frequency range of 0.1Hz to 10kHz, to measure the electrochemical impedance spectroscopy of cathode reaction.Anode is used as reference electrode.
The endurance test of catalyst carrier
In membrane electrode assembly, under 95 ℃, provide under the situation of hydrogen and nitrogen, carry out the accelerated stress test of Pt/ multilayer Bark paper (LBP) at anode and negative electrode respectively.With O 2Oxidizing gas and H 2The relative humidity of fuel gas (RH) is set at 80%, and the back pressure of fuel cell both sides is remained on 20 pounds/square inch.Utilizing potentiostat (Solartron 1280B) that fuel cell is pressed in 1.2 volts kept 200 hours down.According to the rules of aforementioned USDOE (DOE), polarization curve of per 24 hour records under 80 ℃.
The electrochemical properties of Pt/LBP
H by the hydrogen district (0.2 to 0.15 volt) of cyclic voltammogram with respect to saturated calomel electrode 2The integration of absworption peak obtains the electrochemical surface long-pending (ECSA) of Pt/LBP, shown in Fig. 7 (a), has wherein deducted because the electric current that double-deck charging is produced.The electrochemical surface that calculates of Pt/ multilayer Bark paper (LBP) eelctro-catalyst is long-pending to be 56.0m 2/ g and since with Pt/C in the mean P t size compared Pt/ multilayer Bark paper (LBP) of 2.2nm in the Pt particle relatively large, therefore this value is less than the value (70.1m that in commodity Pt/C, obtains 2/ g).Therefore, Fig. 7 (b) shows rotating disk electrode (r.d.e) (RDE) measurement structure, and the limiting current of Pt/ multilayer Bark paper (LBP) catalyst shows the catalytic activity of oxygen reduction reaction lower less than the limiting current of Pt/C catalyst.Yet, consider big Pt particle diameter, the catalyst utilization in Pt/ multilayer Bark paper (LBP) electrode is higher relatively.
Impedance analysis
, experimental data fits to the Randles-Ershler equivalent-circuit model of improvement based on being carried out complex nonlinear least square fitting (CNLS); Utilize the fit procedure (Z-plot that is used for Windows; U.S. Scribner Associates company), impedance spectrum is carried out quantitative analysis.Equivalent-circuit model is shown in Fig. 8 (b), wherein R ΩRepresent Ohmic resistance, R CTRepresent charge transfer resistance, Ws represents finite length Wa Erbao (Warburg) impedance.Replace conventional electric double layer capacitance with normal phase element (CPE), to form non-uniform electrodes.L is pseudo-inductance, and it is with related by the effect that other hardware produced of collector plate, lead-in wire and battery test system.Finite length Wa Erbao (Warburg) impedance meter is shown
Zw(ω)＝Zw(0)[tanh(js) 1/2/(js) 1/2] (3)
Wherein, s=l 2(ω/D), j=(1) 1/2L and D are respectively diffusion length and coefficient.Zw (0) is a resistance to mass tranfer, and it is the value of Zw (ω) when ω → 0.Fig. 8 (a) shows that mensuration is based on (electrochemical impedance spectroscopy) data of the EIS by symbology of the membrane electrode assembly of Pt/LBP, Pt/SF13 and Pt/SF19 and the fitting data of being represented by solid line.
For Pt/ multilayer Bark paper film (LBP), Pt/SF13 and Pt/SF19, the charge transfer resistance RCT that is obtained by fit procedure is respectively 0.15 Ω/cm 2, 0.19 Ω/cm 2With 0.21 Ω/cm 2Because the existence of macropore, the mass transfer resistance among Pt/ multilayer Bark paper film (LBP) and the Pt/SF19 is insignificant (＜10 -9Ω/cm 2).On the contrary, the mass transfer resistance of SF13 catalyst carrier is 0.039 Ω/cm 2, this is because less relatively hole and higher relatively ionomer load cause the oxygen diffusion difficulty.
For the purpose of description, provided foregoing description to the preferred embodiment for the present invention.These descriptions are not intended the present invention is limited to disclosed precise forms.In fact, according to foregoing description, can be easily to the modification and the variation of above description.Therefore, have no intention scope of the present invention is limited to the detailed description that this paper provides.

Claims (20)

1. membrane electrode assembly (310) that is used for fuel cell (100) comprising:
PEM (130); And
Gradient catalyst structure (120 or 140), it comprises a plurality of catalyst nanoparticles that are arranged on the multilayer Bark paper,
Wherein multilayer Bark paper comprises the ground floor and the second layer at least,
Wherein ground floor has the porosity that is lower than the second layer, and
Wherein a plurality of catalyst nanoparticles of first weight percent are arranged on the ground floor, and a plurality of catalyst nanoparticles of second weight percent are arranged on the second layer, and wherein first weight percent is than the big at least 5wt% of second weight percent.
2. membrane electrode assembly according to claim 1 (110), the catalyst utilization of wherein said a plurality of catalyst nanoparticles is≤0.35g Cat/ kW.
3. membrane electrode assembly according to claim 1 (110), wherein ground floor has than the porosity of the second layer low 5% porosity at least.
4. membrane electrode assembly according to claim 1 (110), wherein ground floor comprises (i) and mixture (ii): (i) at least a in SWCN, many walls of the minor diameter nanotube or both and (ii) carbon nano-fiber, many walls of major diameter nanotube or both; And wherein the second layer comprises carbon nano-fiber, many walls of major diameter nanotube or both.
5. membrane electrode assembly according to claim 1 (110), wherein said a plurality of catalyst nanoparticles comprise the element that is selected from down group: platinum, iron, nitrogen, nickel, carbon, cobalt, copper, palladium, ruthenium, rhodium and combination thereof.
6. membrane electrode assembly according to claim 1 (110), wherein said gradient catalyst structure (120 or 140) further comprises perfluorinated sulfonic resin.
7. membrane electrode assembly according to claim 1, wherein gradient catalyst structure (120 or 140) is cathode catalyst layer (140).
8. a proton exchanging film fuel battery (100) comprising:
The film exchange assembly (110) of claim 1, wherein gradient catalyst structure (120 or 140) is cathode catalyst layer (140); And
Anode catalyst layer (120);
Wherein PEM (130) is arranged between cathode catalyst layer (140) and the anode catalyst layer (120).
9. Proton Exchange Membrane Fuel Cells according to claim 8 (100), the catalyst utilization of wherein said a plurality of catalyst nanoparticles is≤0.35g Cat/ kW.
10. Proton Exchange Membrane Fuel Cells according to claim 8 (100), wherein the porosity of the ground floor of multilayer Bark paper hangs down 5% at least than the porosity of the second layer of multilayer Bark paper.
11. Proton Exchange Membrane Fuel Cells according to claim 8 (100) wherein through after forming multilayer Bark paper, a plurality of catalyst nanoparticles being deposited on the multilayer Bark paper, forms cathode catalyst layer (140).
12. Proton Exchange Membrane Fuel Cells according to claim 8 (100), wherein cathode catalyst layer (140) further comprises perfluorinated sulfonic resin, wherein after forming multilayer Bark paper, is coated with perfluorinated sulfonic resin.
13. Proton Exchange Membrane Fuel Cells according to claim 8 (100); Further comprise cathode gas diffusion layer (160), wherein cathode catalyst layer (140) is oriented and makes the ground floor of multilayer Bark paper contact and the second layer of multilayer Bark paper contacts with cathode gas diffusion layer (160) with PEM (130).
14. a method of making the catalyst layer (120 or 140) of fuel cell, this method comprises:
Preparation gradient catalyst structure, this preparation process comprises:
Form multilayer Bark paper, wherein this multilayer Bark paper comprises the ground floor and the second layer at least, and wherein ground floor has the porosity that is lower than the second layer; And
A plurality of catalyst nanoparticles are deposited on the multilayer Bark paper.
15. method according to claim 14, the catalyst utilization of wherein said a plurality of catalyst nanoparticles is≤0.35g Cat/ kW.
16. method according to claim 14, wherein the porosity of the ground floor of multilayer Bark paper than multilayer Bark paper the porosity low at least 5% of the second layer.
17. method according to claim 14, wherein ground floor comprises (i) and mixture (ii): (i) at least a in SWCN, many walls of the minor diameter nanotube or both and (ii) carbon nano-fiber, many walls of major diameter nanotube or both; And wherein the second layer comprises carbon nano-fiber, many walls of major diameter nanotube or both.
18. method according to claim 14, wherein said formation step occurs in before the said deposition step.
19. method according to claim 18; Wherein a plurality of catalyst nanoparticles of first weight percent are arranged on the ground floor; A plurality of catalyst nanoparticles of second weight percent are arranged on the second layer, and wherein first weight percent is than the big at least 10wt% of second weight percent.
20. method according to claim 14 further comprises:
Perfluorinated sulfonic resin is coated on the multilayer Bark paper, and wherein said application step occurs in after the said deposition step.
CN201080004863.6A 2009-07-17 2010-07-19 Catalytic electrode with gradient porosity and catalyst density for fuel cells Expired - Fee Related CN102318111B (en)

Applications Claiming Priority (5)

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